US2462337A - Preparation of unsaturated acid esters - Google Patents
Preparation of unsaturated acid esters Download PDFInfo
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- US2462337A US2462337A US689196A US68919646A US2462337A US 2462337 A US2462337 A US 2462337A US 689196 A US689196 A US 689196A US 68919646 A US68919646 A US 68919646A US 2462337 A US2462337 A US 2462337A
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- 239000002253 acid Substances 0.000 title description 48
- 150000002148 esters Chemical class 0.000 title description 28
- 238000002360 preparation method Methods 0.000 title description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 21
- 238000010992 reflux Methods 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 17
- 150000002430 hydrocarbons Chemical class 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 11
- 239000004334 sorbic acid Substances 0.000 description 11
- 229940075582 sorbic acid Drugs 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 230000032050 esterification Effects 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 9
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 9
- 235000010199 sorbic acid Nutrition 0.000 description 9
- 150000005846 sugar alcohols Polymers 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 8
- 150000002596 lactones Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000021615 conjugation Effects 0.000 description 6
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- -1 alkylene glycols Chemical class 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QKRUPRBAQFNCCY-UHFFFAOYSA-N 3,4-dihydro-2h-oxepin-7-one Chemical class O=C1OCCCC=C1 QKRUPRBAQFNCCY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- LABTWGUMFABVFG-UHFFFAOYSA-N methyl propenyl ketone Chemical compound CC=CC(C)=O LABTWGUMFABVFG-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- IAAPVNQZSBLWKH-ICDJNDDTSA-N (2e,4e,6e)-octa-2,4,6-trienoic acid Chemical compound C\C=C\C=C\C=C\C(O)=O IAAPVNQZSBLWKH-ICDJNDDTSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- YFMGHVQBAINRBB-UHFFFAOYSA-L disodium hydrogen carbonate chloride hydrate Chemical compound C([O-])(O)=O.[Na+].Cl.[OH-].[Na+] YFMGHVQBAINRBB-UHFFFAOYSA-L 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- IAAPVNQZSBLWKH-UHFFFAOYSA-N octatrienoic acid Natural products CC=CC=CC=CC(O)=O IAAPVNQZSBLWKH-UHFFFAOYSA-N 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- WSWCOQWTEOXDQX-MQQKCMAXSA-N sorbic acid group Chemical group C(\C=C\C=C\C)(=O)O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/587—Monocarboxylic acid esters having at least two carbon-to-carbon double bonds
Definitions
- the temperature of the reaction appears fundamental, for with an increase in temperature the rate of polymerization has beenfoun'd to increase faster than that of esterification; low temperatures are thus indicated for preferentiallypromoting esterification.
- the temperature must be sufllciently high to secure vaporization and removal of water as formed in order that the esterification may proceed.
- theesterification can be car-- ried to a useful completion without interference by g elation; preferably, the reaction is continued only to a final refluxing temperature ranging from about 120 C. to 150 C. with the further advantage that discoloration is thereby avoided.
- solvents found particularly suitable are the hydrocarbon thinners, such'as benzene, ethyl benzene, toluene,
- sulfonic acids such as benzeneand toluene-sulfonic acids, operate as stron acids though not as effectively as the mineral acids listed in securing a substantial completion-of the esterification without the initiation of an inhibiting gelation.
- Electrophilic halides such as boron trichldridaaluminum chloride, zinc chloride, and
- thev presence of a substantially water-insoluble organic solvent that vaporizes at a reaction temperature within the catalyst is added in about 1.5 to 2 per cent concentration based on the weight of the reactants.
- Inhibitors of polymerization are helpful, though no inhibitor has been found that permits esterincation to continue to completion in the absence or sumblecontrol; inhibitors are further useful for improving storage stability of the ester products.
- Sulfur has been ,iound particularly eflicient in amounts of from about 0.1 per cent to 0.5 per cent based on the weight of reactants and especially when used in conjunction with sulfuric acid as the catalyst; but selenium, hydroquinone and other known inhibitors can be used.
- Polyhydric alcohols to form the esters include alkylene glycols and polyglycols, glycerols and polyglycerols, erythritol and pentaerythritol and their polymers, sorbitol, mannitol, trimethylolpropane, polyhydroiwethyl-benzenes, etc.; the foregoing can be seen to be primarily alcohols consisting of linked hydrocarbons having hy-,
- the diene monoacids for preparing'the esters, to which this invention is directed are aliphatic acids having ethylenic bonds in conjugation and one of these bonds in conjugation with the carbonyl group; they comprise those acids having a straight chain skeletal structure wherein n is 2 to 4, and those acids having a cross-conjugate chain skeletal structure wherein the indicated free valencies are satisfied by hydrogen, alkyl, alkenyl or aryl groups.
- straight chain acids of primary interest include fi-vinyl-acrylic, octatrien-(2,4,6)-oic, decatetraen-(2,4,6,8) -oic, and p-styryl-acrylic; but a-methyl-sorbic, a-ethylsorbic, 'y-e-dimethyl-sorbic, p-t-dimethyl-sorbic, a-methyl-7-benzal-crotonic, a-ethyl-t-phenyl-abutadiene a carboxylic, 2,6-dimethyl-decatrien-(2,6,8)-oic-(), etc., likewise form esters as herein disclosed.
- cross-conjugate acids examples include a-p-isopropylidene-propionic, avinyl-cinnamic, a-isopropenyl-cinnamic, a-iSO- propenyl furfural-acetic, a-isopropenyl-cinnamenylacrylic, etc.
- An unsaturated straight chain acid corresponding to the foregoing can be prepared by the addition of ketene to a carbonyl compound, such as an unsaturated aldehyde or ketone that, in other words, has the structure where R is either hydrogen or a hydrocarbon radical at low temperature in the presence of an organic solvent and a Friedel-Crafts type of catalyst, particularly boron trifluoride, yielding an unstable ,B-lactone that apparently tends to rearrange to a more stable 7- or t-lactone or to polymerize (according to U. S. patent to. Boese 2,382,464, August 14, 1945) for preparing a crossconjugated acid.
- a carbonyl compound such as an unsaturated aldehyde or ketone that, in other words, has the structure where R is either hydrogen or a hydrocarbon radical at low temperature in the presence of an organic solvent and a Friedel-Crafts type of catalyst, particularly boron trifluoride, yielding an unstable ,
- ketene substituted by an unsaturated grouping can be reacted with a ketone or aldehyde (saturated or unsaturated).
- HY- droiysis (refluxing in caustic soda solution) and deny (nation (with a dehydrating catalyst as suiruric acid) or pyrolysis oi polymeric lactone yields the l p unsaturated acid of which the lactone is the inner ester of the corresponding hyoroxy acid (U. S.
- the mixture was charged into a vessel, agitated and heated to reflux under an atmosphere of carbon dioxide; the vapors were condensed in a trap designed to return the upper hydrocarbon layer to the reaction vessel and to permit withdrawal of the water layer.
- the mass was maintalned at reflux temperature to about 146'-147' C. for 11.5 hours or until water ceased to come off. It was cooled and slowly agitated while adding 100 grams of a solution prepared from Grams Sodium chloride 75 Anhydrous sodium carbonate 35 Distilled water 300 Ethanol (95%) 70 After agitating for 20 minutes, the solution was allowed to separate into layers; the lower layer was drawn off, and the upper layer was dried with calcium chloride and filtered. The final acid number of the non-volatile was 0.56 and the esteriflcation was 98.3 per cent complete and the product was a clear amber in color.
- the charge was heated to reflux under a blanket of carbon dioxide, and the water of esteriflcation was separated; after 6 hours 69.6 per cent of the sorbic acid had esterified.
- the excess acid was neutralized by washing as before with a solution of sodium chloride, anhydrous sodium carbonate, water and alcohol, the aqueous layer was separated, and the hydrocarbon layer dried over anhydrous calcium chloride and filtered.
- the final yield of disorbate of 1,3-dihydroxy propane was 84.1 per cent with an acid number of 4.92.
- Example 5 Sorbic acid grams 840 Pentaerythritol ..do.. as; Toluene do 281 Sulfur do 388 Sulfuric acid .d 20.25 0 Methanol ..mil1i1iters-- 80 A charge 'of the sorbic acid, alcohol, solvent and sulfur was brought to 100 C. while blowing with carbon dioxide, and the sulfuric acid in the methanol was slowly added. The mass was heated to reflux and held for 4 hours to a temperature of 136 C, while removing the water of esteriflcation; at this point the reaction was 84.1 per cent complete, and it was discontinued by diluting with 600 grams of xylene. The mass was washed with a sodium carbonate-sodium chloride-water solution, the aqueous layer separated, and the hydrocarbon layer filteredv and dried.
- the mass was refluxed in an atmosphere of CO: using agitation and a trap separating water and hydrocarbon and designed to return the hydrocarbon to the reaction vessel. After 2.5 hours of refluxing the esteriflcation was 98 per cent complete and the end refluxing temperature was about 136 C. The mass was diluted to 50 per cent non-volatile with more toluene, cooled and filtered. A pale yellow solution resulted which was lighter in color than a similar batch prepared with H2804 as the catalyst.
- Example 8 Crude sorbic intermediate (75% available as sorbic acid) grams 554 Ethylene glycol do- 83 Xylene ..do- 345 Sulfuric acid (95.5%) do 6.15 Sulfur do 1.15 Methanol cubic centimeters 25 l 15% excess.
- ECHO crotonaldehyde
- the residue was mixed with the glycol and the organic solvent, and heat and agitation were applied under at atmosphere of C02.
- the catalyst in methanol solution together with the inhibitor were slowly added at about 94 C.
- the mass was maintained at reflux temperature for approximately 4 hours during which time the final temperature reached was 151 C. and the esterification was about '70 per cent complete.
- the mass was cooled-and washed with sodium carbonatesalt-water to remove any free acid. After separation of the water layer, the mass was dehydrated over calcium chloride and filtered.
- the final ester solution was dark amber in color and free from resin and gel products.
- the esterifying process is thus a self-clarifying one as well as one that eliminates the necessity of the isolation of either the lactone from the intermediate or the unsaturated acid before reacting with the alcohol. It thus affords a cheap method of preparing a synthetic oil with drying or polymerizing properties and having particular utility in the preparation of oil-modified resinous compositions for molding into brake linings, insulation, etc., and for coatings where color is not objectionable.
- Example 9 A lactone, identified as 3-methyl-hexenolide (1,4) was prepared along with 3-methyl-hexenolide (1,5) by reacting ethylidene acetone with ketene. The hexenolides wereseparated, and the hexenolide (1,4) having the structure was used in this example; this lactone opens to produce 3-methl-sorbic acid. The equipment and processing was as before with a charge of 1 10% excess.
- Example 10 When the S-methyl hexenolide (1.5) was substituted'in Example 9 under identical conditions a product of surprisingly much lighter color and 90.8 per cent esterification resulted.
- This lactone has the structure CH: O
- the polyhydric alcohol sorbates and other esters or this invention are characterized by a very rapid drying in air and by producing extremely hard films that are water and alkali resistant.
- esters have numerous applications, such as in wrinkle finishes; furniture finishes; blends with varnishes and oils to promote rapidity of drying and hardness; paper saturants; laminating and surface sheet materials; cloth sizing; and blends and hardeners for liquid polystyrene, nitrocellulose, vinyl chloride-vinyl acetate copolymers and their hydrolyzed products, polyvinyl butyral, alkyd resins, etc.
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Description
aw he Patented Feb. 22, 1949 UNITED STATES PATENT OFFICE PREPARATION ORUNSA'I'URATED a ACID E STERS Leon Shechter, Em am, 1., mum to Bakelite Corporation, a corporation of New Jersey No Drawing. Application August 8,1946, Seriai'No. 689,196
Moreover, so far as known, only the glycol sorbates .of this group of esters have heretoforefbeen obtained, and theseonly'by resort to indirect methods that involve an intermediate step of chlorination; direct reaction-however, is preferredasit avoids the need of separating objectionable by products and for corrosione-resistance reaction vessels. i v It has now beendiscovered'that, while factors 6 Claims. (Cl.'.260'486) above mentioned refluxing temperature range has been found convenient and eflectivein functioning as an agent both to slow the polymerization or gelation and to speed theesterification by increasing the rate of water take-off; in general the solvent forms an azeotropic mixture with the water; "The proportion of solvent added does not appear critical, for as little as 5 per cent of solvent has-been found'sufilcient when the other conditions are observed, and the smaller the amount of solvent, within limits .of roughly,5-25 per cent, the fasteris the esteriflcation rate; but 25-75 per -cent of solvent can be present in the reaction -'mass,-andthelesterification in'general will still p'roceey:l;-,to substantial completion without gela- 'tion;i in this respectlthe dihydric alcohols, which possess-lower functionality, permit wider latitude :q'asto range' of'fclilutlon' than dothe -triand higher which influence the rate of direct esterification-.- such as temperature, solvent control, reactant concentration, catalyst, speed of water removal and agitationalso affect the rate of polymeriza tion, these factors do not operate to the same degree or in a like manner in the two reactions.
With this discovery as a basisyithasbeenlfound possible to so select the conditions that substantially complete esterific'ation can be had without interference by gelling due to polymerization. Polyhydric alcohol esters of conjugated double bondmonoacids-a's defined abovehaveas a-resultbeen "successfully I prepared :bydirect "-ire'ac'tionx They are useful as substitutes for naturaloils in coating and other compositions.
Among the controlling conditions, that of the temperature of the reaction appears fundamental, for with an increase in temperature the rate of polymerization has beenfoun'd to increase faster than that of esterification; low temperatures are thus indicated for preferentiallypromoting esterification. On the other hand, the temperature must be sufllciently high to secure vaporization and removal of water as formed in order that the esterification may proceed. In general, it has been'found that by holding the temperature below about 170 C. when other, controlling factors are carefully observed, theesterification can be car-- ried to a useful completion without interference by g elation; preferably, the reaction is continued only to a final refluxing temperature ranging from about 120 C. to 150 C. with the further advantage that discoloration is thereby avoided.
polyhydricalcohols; For the purpose; solvents found particularly suitable are the hydrocarbon thinners, such'as benzene, ethyl benzene, toluene,
xylene, etc., Solvesso, Hexone," o-bromtoluene,
diisobutyl ketone,ldichloroethyl ether, and the like. -It has also'beenfound essential to the preferential promotion;of 'esterification over polymeriza- 'tion that an agen't having a strong promoting action'iinthe organic solvent medium be present "as a catalyst"; the'order of strength is determined by" the relative speeds 'of the ester-forming reac- .fsontiont- Particularly iuseru1.-. as stron condensing 7 agents -arethe mineral acids: that in 'the @order s'of Jdecrea'sing strength: appear to be perchloric,
- sulfuric, hydrochloric, nitric, etc of these sulfuric acid is preferred for availability and the high order-of strength that promotes a substantial completion of the esteriflcation in the preferred temperature range without objectionable gelling in as little as 5 per cent of solvent, such as xylene or toluene. The sulfonic acids, such as benzeneand toluene-sulfonic acids, operate as stron acids though not as effectively as the mineral acids listed in securing a substantial completion-of the esterification without the initiation of an inhibiting gelation. Electrophilic halides,-such as boron trichldridaaluminum chloride, zinc chloride, and
yparticularly boron" triiluor'ide, likewise act :as
strong acids in catalyzing the condensation reaction (Physical Organic'Ch'emistry,1940,by Hammett, page 261) When sulfuric acid is used, the
For holding the temperature Within the desired range during the reaction, thev presence of a substantially water-insoluble organic solvent that vaporizes at a reaction temperature within the catalyst is added in about 1.5 to 2 per cent concentration based on the weight of the reactants.
'thoughfrom 0.3 to 3.0 per cent can beemployed with good effect; the other acids and thehalides operating as acids are used in equivalent proportions in .inverseratio to their order of strength.
Inhibitors of polymerization are helpful, though no inhibitor has been found that permits esterincation to continue to completion in the absence or soiventcontrol; inhibitors are further useful for improving storage stability of the ester products. Sulfur has been ,iound particularly eflicient in amounts of from about 0.1 per cent to 0.5 per cent based on the weight of reactants and especially when used in conjunction with sulfuric acid as the catalyst; but selenium, hydroquinone and other known inhibitors can be used.
Polyhydric alcohols to form the esters include alkylene glycols and polyglycols, glycerols and polyglycerols, erythritol and pentaerythritol and their polymers, sorbitol, mannitol, trimethylolpropane, polyhydroiwethyl-benzenes, etc.; the foregoing can be seen to be primarily alcohols consisting of linked hydrocarbons having hy-,
droxyl replacements for hydrogen atoms on different carbon atoms, though in polymerized form they may take on an ether structure as a result of condensation and dehydration. Normally the alcohol is present in excess of stoichiometric proportions.
The diene monoacids for preparing'the esters, to which this invention is directed, are aliphatic acids having ethylenic bonds in conjugation and one of these bonds in conjugation with the carbonyl group; they comprise those acids having a straight chain skeletal structure wherein n is 2 to 4, and those acids having a cross-conjugate chain skeletal structure wherein the indicated free valencies are satisfied by hydrogen, alkyl, alkenyl or aryl groups. In addition to sorbic acid, straight chain acids of primary interest include fi-vinyl-acrylic, octatrien-(2,4,6)-oic, decatetraen-(2,4,6,8) -oic, and p-styryl-acrylic; but a-methyl-sorbic, a-ethylsorbic, 'y-e-dimethyl-sorbic, p-t-dimethyl-sorbic, a-methyl-7-benzal-crotonic, a-ethyl-t-phenyl-abutadiene a carboxylic, 2,6-dimethyl-decatrien-(2,6,8)-oic-(), etc., likewise form esters as herein disclosed. Examples of the cross-conjugate acids are a-p-isopropylidene-propionic, avinyl-cinnamic, a-isopropenyl-cinnamic, a-iSO- propenyl furfural-acetic, a-isopropenyl-cinnamenylacrylic, etc.
An unsaturated straight chain acid corresponding to the foregoing, can be prepared by the addition of ketene to a carbonyl compound, such as an unsaturated aldehyde or ketone that, in other words, has the structure where R is either hydrogen or a hydrocarbon radical at low temperature in the presence of an organic solvent and a Friedel-Crafts type of catalyst, particularly boron trifluoride, yielding an unstable ,B-lactone that apparently tends to rearrange to a more stable 7- or t-lactone or to polymerize (according to U. S. patent to. Boese 2,382,464, August 14, 1945) for preparing a crossconjugated acid. ketene substituted by an unsaturated grouping can be reacted with a ketone or aldehyde (saturated or unsaturated). HY- droiysis (refluxing in caustic soda solution) and deny (nation (with a dehydrating catalyst as suiruric acid) or pyrolysis oi polymeric lactone yields the l p unsaturated acid of which the lactone is the inner ester of the corresponding hyoroxy acid (U. S. patents to Kung 2,356,459, August 22, 1944 and 2,361,036, October 24, 1844) the other'etnyienic bonds of the unsaturated acid sougnt are supplied, by corresponding radicals on either-the -ketene or carbonyl compound or both, such radicals being the alkyl, aikenyl, aralkyl and aryl groups.
The isolation of the acid from the intermediate and its purification, however, is not readily accomplished. According to Kung (2,381,036, third paragraph) hydrolysis and dehydration do not give good yields because of the instability of a lactone and inability to dehydrate adequately; and the isolation and subsequent polymerization of the monomeric lactone as suggested by Kung (2,356,459) places a limitation on the original reactants and reacting conditions. In any case there is involved the separation of the acid that on account of its unsaturation tends to form resinous or other by-products if its distillation or fractionation is attempted.
It has been proposed to isolate the unsaturated acid obtained in the addition of a ketene to a carbonyl compound by esterifying the acid with a monohydric alcohol, distilling oi! the ester and then freeing the acid by saponiflcation; so long as the ester is of a volatile or distillable character, such a process can be practiced, though it is relatively expensive and tedious. Polyhydrlc alcohol esters, however, do not lend themselves to separation from the non-volatiles by distillation, and it has accordingly appeared necessary to isolate the acids first before proceeding with the esteriflcation. Most surprising, therefore, it has now been found that, when the intermediate is reacted in place of the acid with a polyhydric alcohol in a solvent and in the presence of a strong acid catalyst in accordance with this invention, a reaction occurs in which the intermediate evidently opens and rearranges to the unsaturated acid, and under the conditions, resinitication or polymerization is sufllciently inhibited to yield an ester product that can then be separated by neutralizing, washing and drying similar to the ester prepared from the isolated acid. This procedure greatly reduces the cost as well as simplifies the procedure by the omission of the steps of isolating and purifying the acid to yield a synthetic, unsaturated oil.
The following examples are illustrative of without limiting the invention. thereto.
The mixture was charged into a vessel, agitated and heated to reflux under an atmosphere of carbon dioxide; the vapors were condensed in a trap designed to return the upper hydrocarbon layer to the reaction vessel and to permit withdrawal of the water layer. The mass was maintalned at reflux temperature to about 146'-147' C. for 11.5 hours or until water ceased to come off. It was cooled and slowly agitated while adding 100 grams of a solution prepared from Grams Sodium chloride 75 Anhydrous sodium carbonate 35 Distilled water 300 Ethanol (95%) 70 After agitating for 20 minutes, the solution was allowed to separate into layers; the lower layer was drawn off, and the upper layer was dried with calcium chloride and filtered. The final acid number of the non-volatile was 0.56 and the esteriflcation was 98.3 per cent complete and the product was a clear amber in color.
Example 2 Grams Ethylene glycol 105 Sorbic acid 336 Xylene 900 Sulfuric acid (conc.) 8 Sulfur 1.5
Example 3 Grams 1,3 dihydroxypropane 125.4 Sorbic acid 336 Xylene 922.8 p-Toluene sulfonic acid 10 Sulfur 1.5
The charge was heated to reflux under a blanket of carbon dioxide, and the water of esteriflcation was separated; after 6 hours 69.6 per cent of the sorbic acid had esterified. To hasten the reaction there was added 5 grams of concentrated sulfuric acid; after an additional 5 hours of refluxing to a temperature of 146-147 C. the esterification was 88.5 per cent complete. The excess acid was neutralized by washing as before with a solution of sodium chloride, anhydrous sodium carbonate, water and alcohol, the aqueous layer was separated, and the hydrocarbon layer dried over anhydrous calcium chloride and filtered. The final yield of disorbate of 1,3-dihydroxy propane was 84.1 per cent with an acid number of 4.92.
Example 4 Grams Sorbic acid 1,282 Glycerol (98%) 397 Toluene 422 Sulfuric acid (conc;) 13.! Water 27.4
complete as determined by the acid number after making allowance for the acid number attributable to the sulfuric acid; continuing the reaction. for a total of about 6 hours gave 96-99 per out 5 esteriflcation without gelation. The batch was thinned with toluene, and anhydrous sodium carbonate was added to neutralize the acid whereupon the solution was agitated and flltered.'
The batch, thinned with solvent to about 60 per 10 cent non-volatile, had a final acid number of 21.8 on the'non-volatile and a color of 10+ on the Gardner scale.
Example 5 Sorbic acid grams 840 Pentaerythritol ..do.. as; Toluene do 281 Sulfur do 388 Sulfuric acid .d 20.25 0 Methanol ..mil1i1iters-- 80 A charge 'of the sorbic acid, alcohol, solvent and sulfur was brought to 100 C. while blowing with carbon dioxide, and the sulfuric acid in the methanol was slowly added. The mass was heated to reflux and held for 4 hours to a temperature of 136 C, while removing the water of esteriflcation; at this point the reaction was 84.1 per cent complete, and it was discontinued by diluting with 600 grams of xylene. The mass was washed with a sodium carbonate-sodium chloride-water solution, the aqueous layer separated, and the hydrocarbon layer filteredv and dried.
Example 6 Sorblc acid grams 336 Glycerol (98%) do 108.4 Toluene do 100 Boron trifluoride-ether complex cc 9 Approximately 0.9% BF; on sorblc'glycerol reactants.
The mass was refluxed in an atmosphere of CO: using agitation and a trap separating water and hydrocarbon and designed to return the hydrocarbon to the reaction vessel. After 2.5 hours of refluxing the esteriflcation was 98 per cent complete and the end refluxing temperature was about 136 C. The mass was diluted to 50 per cent non-volatile with more toluene, cooled and filtered. A pale yellow solution resulted which was lighter in color than a similar batch prepared with H2804 as the catalyst.
The foregoing examples are directed to sorbic acid; but the other diene monoacids comprehended by this invention behave in the same manner to form esters. This is demonstrated by the following example to octatrienolc acid.
Example 7 Grams Octatrienoic acid 414 Glycerol (98%) 103 Toluene 130 Sulfuric acid (95.5%) 7.! Methanol 7.7
Using the same equipment and following the same procedure as before, the charge of acid, glycerol and solvent had slowly added thereto the sulfuric acid catalyst in methanol whereupon heat was applied to the refluxing temperature. Heating was continued for 6 hours with removal of water of esteriflcation and return of hydrocarbon at the refluxing temperature of about 136 C. At the end of the period the esteriflcation was 91 per cent complete. As before the amass? the reaction of a ketene and a carbonyl compound are the following examples.
Example 8 Crude sorbic intermediate (75% available as sorbic acid) grams 554 Ethylene glycol do- 83 Xylene ..do- 345 Sulfuric acid (95.5%) do 6.15 Sulfur do 1.15 Methanol cubic centimeters 25 l 15% excess.
The crude sorbic intermediate was obtained by passing at about 5-10 C. equimolecular proportions of crotonaldehyde (ECHO wherein R. is the propenyl radical CHa-CH=CH-) and ketene (CH:=CO) through toluene withboron trifluoride as the catalyst; upon stripp the solvent a black viscous residue remained.
The residue was mixed with the glycol and the organic solvent, and heat and agitation were applied under at atmosphere of C02. The catalyst in methanol solution together with the inhibitor were slowly added at about 94 C. The mass was maintained at reflux temperature for approximately 4 hours during which time the final temperature reached was 151 C. and the esterification was about '70 per cent complete. The mass was cooled-and washed with sodium carbonatesalt-water to remove any free acid. After separation of the water layer, the mass was dehydrated over calcium chloride and filtered. The final ester solution was dark amber in color and free from resin and gel products.
The esterifying process is thus a self-clarifying one as well as one that eliminates the necessity of the isolation of either the lactone from the intermediate or the unsaturated acid before reacting with the alcohol. It thus affords a cheap method of preparing a synthetic oil with drying or polymerizing properties and having particular utility in the preparation of oil-modified resinous compositions for molding into brake linings, insulation, etc., and for coatings where color is not objectionable.
Example 9 A lactone, identified as 3-methyl-hexenolide (1,4) was prepared along with 3-methyl-hexenolide (1,5) by reacting ethylidene acetone with ketene. The hexenolides wereseparated, and the hexenolide (1,4) having the structure was used in this example; this lactone opens to produce 3-methl-sorbic acid. The equipment and processing was as before with a charge of 1 10% excess.
The sulfuric acid in methanol was added to the 8 mixture of the remaining ingredients heated to 96' C. The mass was refluxed with return oi solvent. Aiter 7 hours refluxing theesterification was 84 per cent complete. The product was diluted with toluene to 60 per cent non-volatile, giving a dark brown solution.
Immple 10 When the S-methyl hexenolide (1.5) was substituted'in Example 9 under identical conditions a product of surprisingly much lighter color and 90.8 per cent esterification resulted. This lactone has the structure CH: O
CHa-OH-CHg- =OII- The triglycerides of S-methyl-sorbic acid produced in Examples 9 and 10 were found to convert on heating to hard thermoset films much more slowly than straight glyceryl trisorbate. This is due to the decreased reactivity resulting from the replacement of hydrogen by a methyl group in the conjugated structure.
The limiting conditions necessary to esteriiication without undue inhibiting gelation were determined b an extended series of experiments varying the solvent and solvent proportions, catalyst, inhibitor and final reflux temperature that led to the conclusion herein expressed concerning these-factors. In the course of the experiments it was noted that measuring the evolved water was an unreliable method for determining the extent of esterification: but the acid number determinations were in close agreement with the hydroxyl determinations, and the acid number was accordingly selected as an indicator of the extent of esteriflcation.
The polyhydric alcohol sorbates and other esters or this invention are characterized by a very rapid drying in air and by producing extremely hard films that are water and alkali resistant. As an instance, a film of glyceryl trisorbate (Example 4) upon air-drying withstood 5 per cent caustic for 96 hours, and similar tests indicated excellent resistance to 5 per cent acetic acid solution and 3 per cent citric acid solution.
The esters have numerous applications, such as in wrinkle finishes; furniture finishes; blends with varnishes and oils to promote rapidity of drying and hardness; paper saturants; laminating and surface sheet materials; cloth sizing; and blends and hardeners for liquid polystyrene, nitrocellulose, vinyl chloride-vinyl acetate copolymers and their hydrolyzed products, polyvinyl butyral, alkyd resins, etc.
What is claimed is:
1. Process of preparing an ester of a polyhydric alcohol consisting of linked hydrocarbons having hydroxyl replacements for hydrogen atoms on diflerent carbon atoms and an unsaturated monocarboxylic acid having conjugated ethylenic bonds and one of these bonds in conjugation with the acidic carbonyl which comprises directly reacting the acid with an excess over stoichiometric proportions of the alcohol in the presence of a strong acidic catalyst and in an organic solvent therefor at refluxing temperature not exceeding 170 C. to thereby yield esters characterized by drying to hard films.
2. Process of preparing an ester of a polyhydric alcohol consisting of linked hydrocarbons having hydroxyl replacements for hydrogen atoms on diiferent carbon atoms and an unsaturated monocarboxylie acid having coniugated presence of a strong acidic catalyst and in from to 75 per cent by weight of the reactants of an organic solvent therefor at refluxing temperature not exceeding 170 C. to thereby yield esters characterized by drying to hard films.
3. Process of preparing an ester of a polyhydric alcohol consisting of linked hydrocarbons having hydroxyl replacements for hydrogen atoms on clifierent carbon atoms and an unsaturated monocarboxylic acid having conjugated ethylenic bonds and one of these in conjugation with the acidic carbonyl which comprises directly reacting the acid with an excess over stoichiometric proportions of the alcohol in the presence of sulfuric acid and from 5 to 75 per cent by weight of the reactants of a hydrocarbon thinner at refluxing temperature not exceeding 170 C. to thereby yield esters characterized by drying to hard films.
4. Process of preparing an ester of a polyhydric alcohol consisting of linked hydrocarbons having hydroxyl replacements for hydrogen atoms on different carbon atoms and an unsaturated monocarboxylic acid having conjugated ethylenic bonds and one of these in conjugation with the acidic carbonyl which comprises directly reacting the acid with an excess over stoichiometric proportions of the alcohol in the presence of a strong acidic catalyst, of a polymerizing inhibitor and of from 5 to .75 per cent by weight of the reactants of an organic solvent therefor at refluxing temperature not exceeding 170 C. to thereby yield ester characterized by drying to hard films.
5. Process of preparing an ester of a polyhydrlc alcohol consisting of linked hydrocarbons having hydroxyl replacements for hydrogen atoms on diiTerent carbon atoms and an unsaturated monocarboxylic acid having conjugated ethylenic bonds and one of these in conjugation with the carbonyl which comprises directly reacting the acid with 'an excess over stoichiometric proportions of the alcohol in the presence of sulfuric acid, sulfur and of from 5 to per cent by Weight of the reactants of a hydrocarbon thinner at a refluxing temperature not exceeding 170 C. to thereby yield esters characterized by drying to hard films.
6. Process of preparing an ester of glycerol and sorbic acid which comprises directly reacting the.
acid with an excess over stiochiometric proportions of the glycerol in the presence of from 0.3 to 3.0 per cent sulfuric acid, of from 0.1 to 0.5 per cent sulfur and of from 5 to 25 per cent of a hydrocarbon thinner at a refluxing temperature ranging from about to C., the proportions being based on the weight of the reactants to thereby yield esters characterized by drying to hard films.
. LEON SHECHTER.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,129,722 Woodhouse Sept. 13, 1938 2,376,704 Kung May 22, 1945 2,381,880 Cupery Aug. 14, 1945 FOREIGN PATENTS Number Country Date 795,616 France Mar. 18, 1936
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US689196A US2462337A (en) | 1946-08-08 | 1946-08-08 | Preparation of unsaturated acid esters |
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US689196A US2462337A (en) | 1946-08-08 | 1946-08-08 | Preparation of unsaturated acid esters |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2589459A (en) * | 1946-09-04 | 1952-03-18 | Union Carbide & Carbon Corp | Production of surfaced core material |
US2648617A (en) * | 1948-09-02 | 1953-08-11 | Union Carbide & Carbon Corp | Filter medium and method of making the same |
US2780632A (en) * | 1954-06-09 | 1957-02-05 | Eastman Kodak Co | Continuous liquid phase process for effecting condensation of an aldehyde and a carboxylic compound containing an active methylene group |
US4160769A (en) * | 1977-12-12 | 1979-07-10 | Union Carbide Corporation | Oxidation of ketones to esters |
US4183863A (en) * | 1978-04-18 | 1980-01-15 | Union Carbide Corporation | Conversion of cyclohexanol to ε-caprolactone |
WO2015135927A1 (en) * | 2014-03-10 | 2015-09-17 | Giuliani S.P.A. | Compounds with a combined antioxidant activity against free radicals together with an anti-inflammatory action, and pharmaceutical and cosmetic compositions containing them for the treatment of skin and hair |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR795616A (en) * | 1934-07-26 | 1936-03-18 | Fr Duco Soc | Preparation of esters and of compositions containing them |
US2129722A (en) * | 1934-07-14 | 1938-09-13 | Du Pont | Esters of methacrylic acid |
US2376704A (en) * | 1943-10-01 | 1945-05-22 | Goodrich Co B F | Preparation of esters of alpha-beta unsaturated monocarboxylic acids |
US2381880A (en) * | 1940-12-30 | 1945-08-14 | Du Pont | Ester |
-
1946
- 1946-08-08 US US689196A patent/US2462337A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2129722A (en) * | 1934-07-14 | 1938-09-13 | Du Pont | Esters of methacrylic acid |
FR795616A (en) * | 1934-07-26 | 1936-03-18 | Fr Duco Soc | Preparation of esters and of compositions containing them |
US2381880A (en) * | 1940-12-30 | 1945-08-14 | Du Pont | Ester |
US2376704A (en) * | 1943-10-01 | 1945-05-22 | Goodrich Co B F | Preparation of esters of alpha-beta unsaturated monocarboxylic acids |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2589459A (en) * | 1946-09-04 | 1952-03-18 | Union Carbide & Carbon Corp | Production of surfaced core material |
US2648617A (en) * | 1948-09-02 | 1953-08-11 | Union Carbide & Carbon Corp | Filter medium and method of making the same |
US2780632A (en) * | 1954-06-09 | 1957-02-05 | Eastman Kodak Co | Continuous liquid phase process for effecting condensation of an aldehyde and a carboxylic compound containing an active methylene group |
US4160769A (en) * | 1977-12-12 | 1979-07-10 | Union Carbide Corporation | Oxidation of ketones to esters |
US4183863A (en) * | 1978-04-18 | 1980-01-15 | Union Carbide Corporation | Conversion of cyclohexanol to ε-caprolactone |
WO2015135927A1 (en) * | 2014-03-10 | 2015-09-17 | Giuliani S.P.A. | Compounds with a combined antioxidant activity against free radicals together with an anti-inflammatory action, and pharmaceutical and cosmetic compositions containing them for the treatment of skin and hair |
US9738682B2 (en) | 2014-03-10 | 2017-08-22 | Giuliani S.P.A. | Compounds with a combined antioxidant activity against free radicals together with an anti-inflammatory action, and pharmaceutical and cosmetic compositions containing them for the treatment of skin and hair |
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